Detergent for toilet use containing incompletely esterified polyhydric alcohol



Patented Oct. 10, 1939 DETERGENT FOR TOILET USE CONTAIN- lNG INCOMPLETELY ESTEBIFIED POLY- HYDRIC ALCOHOL Robert A. Duncan, Wyomlng,-hio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing.

15 Claims.

This application is a continuatlon-in-part of my co-pending application Serial No. 705,822, filed January 8, 1934.

This invention relates to a substantially soap- 5 free detergent in the form of a bar, which has highly advantageous properties for ordinary toilet and bath use.

The only detergent commonly used in bar form heretofore has been soap of various kinds, the most desirable form for toilet purposes being a milled bar, that is, a soap which has been dried to about ten to fifteen per cent moisture, then mixed and milled to smooth and homogenize the soap, and finally compressed into the form of a bar of suitable size and. shape under high pressure and moderate temperature. This form of soap has a smooth feel, is readily soluble-thus giving a rapid and copious lather, is not unduly wasteful in washstand use, and because of the low temperature and other conditions of making the bar, permits the use of many delicate and desirable perfumes which can be mixed in only at low temperatures.

I have found that a detergent product possessing not only all the desirable properties for toilet and bath use inherent in a milled soap but also other highly advantageous properties, and especially suitable for use in hard water, can be produced when certain detergent agents consisting 0 of the water-soluble salts of sulfonated or sulfated compounds are blended with a suitable quantity of a polyhydric alcohol incompletely esterified with a saturated fatty acid containin twelve or more carbon atoms in the molecule, 5 then milled and pressed into the shape of a bar of suitable size. The sulfonated or sulfated detergent agents that are especially useful in making my product are the substantially solid water-soluble salts of any of those included in the following group, or any mixture of same, the alkyl radicals in all cases having more han eight carbon atoms: the sulfonated and sulfated aliphatic alcohols, the sulfonated and sulfated aliphatic hydrocarbons, fatty acid esters of hydroxy ethyl sulfonic acid,

the fatty acid amide of methyl amino ethyl sulfonic-acid, the fatty acid esters of dihydroxy propyl sulfonic acid, and the high molecular alkyl ethers of dihydroxy propyl sulfonic acid. Of

course there are water-soluble salts of other sulfuric reaction products of high molecular weight organic compounds which are characterized by their high solubility in water, their resistance to precipitation by the constituents of hard water,

and their excellent detergent properties, All of Application January 25, 1936, Serial No. 60,891

these products fall within the scope of my invention. In the specification and claims reference to sulfuric reaction products and sulfonated or sulfated products does not necessarily mean that the product is prepared with the use 5 of sulfuric acid or other sulfonating or sulfating agents. I use this terminology to designate broadly those compounds which'contain an SOaH group with the sulfur atom attached to a carbon atom either directly or through an oxygen atom linkage.

Those sulfonated and sulfated compounds which I prefer to use are the water-soluble salts of the sulfonated and/or sulfated alcohols obtainable from the natural fats and fatty oils (oils of 15 the coconut all type characterized by their high saponiflcation number, for example, coconut oil and palm kernel oil, being of especial value), the oleic acid ester of hydroxy ethyl sulfonic acid, the oleic acid amide of methyl amino ethyl sulfonic 2() acid, and the coconut oil fatty acid ester of dihydroxy propyl sulfonic acid.

The above mentioned sulfonated or sulfated detergent agents are ordinarily available in the form of a powder or other substantially solid 5 form, usually containing some sodium sulfate and/or sodium chloride. If available in the form of a bar, they would show some highly advantageous properties, but they would be so readily soluble in ordinary washstand use as to produce 30 an unnecessarily copious lather, to become soft and slimy inremaining on the washstand' after use, and to be uneconomical in general. If a material could be added to these detergents which would not interfere with their usual sudsing and 5 detergent properties and which would not impart a harsh or otherwise disagreeable feel to the product, but would reduce the solubility and assist in binding the particles together in forming the bar, a more desirable and useful product 40 would result. There are many products of less solubility which would not effect sudsing and detergent action when used with such sulfonated or sulfated organic substances, but which leave the product with a gritty feel. There are many 45 which would not leave a gritty feel, but which would react against detergency and sudsing and these in general include the common superfatting agents for soap. There are substances of both the above types which would not have any de- 5 sirable effect in binding the sulfate or sulfonate in bar form. There are substanceswhich could -be used as diluents, but whose rate of solubility is toogreat or too low.

After an extended investigation, I have dis- 55 covered that certain polyhydric alcohols incompletely esterified with saturated fatty acids having twelve or more carbon atoms in the fatty acid radical, such as the high molecular saturated fatty acid monoand di-esters of glycerin (sometimes referred to as superglycerinated fats) and the higher molecular saturated fatty acid monoesters of ethylene glycol, will quite satisfactorily provide the desired characteristics. ,The words "superglycerinated fat as used herein are intended to mean the reaction product of a triglyceride fat and glycerin in suitable proportions to produce monoand/or diglycerides, or the reaction product of a higher fatty acid and glycerin in suitable proportions to form an incompletely esterified product consisting essentially 'of monoand/or diglycerides. The saturated superglycerinated fats may be prepared from a suitable saturated triglyceride fat, or from a suitable saturated higher fatty acid, or by other known means. Furthermore, it should be understood that the word saturated as used herein includes within its meaning the substantially saturated products having iodine numbers not higher than about 15 or 20 as well as the completely saturated products.

These saturated incompletely esterified polyhydric alcohols are of low solubility, help to bind the sulfonate or sulfate together in a bar, do not give a harsh or gritty feel, and do not interfere seriously with detergency and sudsing. I find that the monoglyceride of commercial stearic acid is especially suitable for this purpose because of its especially desirable properties, its ready availability, and its relatively low cost. It will be understood that I do not use the saturated ini completely esterified polyhydric alcohols as superfatting agents, nor do these compoundsin fact serve this purpose. Those versed in the art are aware that superfatting agents are used in soap compositions to improve characteristics of same. hand, I use a saturated superglycerinated fat, or similar compound, in a sulfonated or sulfated detergent composition for the opposite effect, that is, for thepurpose of decreasing the solubility of same and of simultaneously binding same together in the form of a bar satisfactory for washstand and zailet use. Most of the common superfatting agents for soap, for example tailow,

lanolin, wool fat and the like, are unsuitable for my purpose. Furthermore, it will be apparent from the description of my invention that in most cases I use much more saturated incompletely esterified polyhydric alcohol that would be used for superfatting purposes. I find that in order to effectively accomplish my object Imust use an amount in excess of five per cent, it being understood that proportions given here and elsewhere in the specification and claims are by weight. In its broadest aspects, however, my invention covers compositions containing an amount of saturated partially esterifled polyhydric alcohol sufllcient to produce a detergent bar having the same solubility as a bar of ordinary milled toilet soap under the same conditions of use.

In using the monoglyceride of stearic acid, for example, or other saturated incompletely esterified polyhydric alcohol," I usually employ from about eight per cent to about sixty per cent in a mixture with about ninety-two per cent to. about forty per cent of the commercial sulfonated or sulfated detergent. The optimum amount of saturated incompletely esterified polyhydric alcohol to be used in admixture with the sulfuric reuse to any objectionable extent.

In the instant invention, on the otherv action. product will, of course, depend on the characteristics of the particular sulfuric reaction product being used and the firmness and solubility desired in the product. Thus it will be noted that the ratio of the sulfonated or sulfated detergent salt to the saturated incompletely esterified polyhydric alcohol may vary, for example, from about 11.5:1 to about 0.67:1. These materials are mixed together in dry condition, are

milled in the usual milling apparatus commonly used in the manufacture of high-grade toilet soaps, any perfume or desired ingredients being simultaneously incorporated, and the mixture after mixing is then passed through the plodder or otherwise converted into bar form by known means.

The products formed in the practice of my invention have remarkable sudsing and detergent properties even in hard water, possess a smooth feel, dissolve readily, give a copious lather but do not waste away in use nearly as rapidly as the detergent without the added saturated incompletely esterified polyhydric alcohol and do not get soggy or smeary on the washstand after My products have greater sudsing and detergent power than ordinary milled soaps and do not cause any precipitate, 'even in hard waters, and therefore do not form a ring of dirt or insoluble soaps around a lavatory or bath tub, like ordinary soaps do. The incompletely esterified polyhydric alcohols mentioned also serve to reduce the cost of the product, thus making it more economical as well as advantageous in use.

The following examples will further illustrate the nature of my invention, but it will be understood that I am not restricted thereto.

'Earample 1.Ninety parts of the powdered neutral sodium salt of the reaction product of concentrated sulfuric acid on the higher alcohols obtainable from coconut oil are mixed with 10 parts of superglycerinated fat (monoand/or diglycerides) prepared from substantially completely hydrogenated cottonseed oil. The mixture is milled in the well known manner, plodded, and pressed into a cake of suitable size and shape.

Example 2.--Seventy parts of the ammonium salt of the oleic acid ester of hydroxy ethyl sulfonic acid and parts of the monoglyceride prepared from commercial stearic acid are thoroughly mixed, milled, plodded, and stamped into any desired form.

Example 3.-Eight parts by weight of the sodium salt of the oleic acid amide of methyl amino ethyl sulfonic acid and 20 parts by weight of the superglycerinated fat prepared from stearic acid are processed as in Example 2.

Erample 4.Seventyfive parts of the sulfated detergent used in Example 1 are mixed with 25 parts of the mono-ester of ethylene glycol and commercial stearic acid. The mixture is milled, plodded, and stamped into the form of an ordinary cake'of milled toilet soap.

The products of the above examples behave substantially like good milled toilet soap in permanence of bar form and in lathering and detergent qualities in use. They are much superior to ordinary milled toilet soap when employed in hard water, in that they do not form insoluble salts with the constituents imparting hardness to the water. They do not become slimy on the washstand, nor do they waste away rapidly in use as would be the case were the incompletely esterifled polyhydric alcohols not present. 1

It will noted that the proportions of sulfonated or sulfated detergent and the partially esterified polyhydric alcohol vary in the examples. This variation is dependent on the type of sulfonated or sulfated detergent used, the properties of said detergent, the type of partially esterifled polyhydric alcohol used, and also on the hardness of the water in which the product is intended to be used. It is desirable to use more of the superglycerinated fat or its equivalent for the new product when intended to be used in hard water territories, since in such waters milled bar soap is rather wastefully employed and the experience of the housewife will demand a product of our type of correspondingly reduced solubility.

In the use of the term solubility in the specification and claims, I do not mean the total amount that can be made to dissolve in water,"

but rather the rate of solution or the time required under ordinary conditions of use to dissolve a suflicient quantity to accomplish the required detergent work.

Having thus described my invention, what-I claim and desire to secure by Letters Patentis:

l. A detergent in bar form substantially free from soap containing essentially a mixture of more than five per cent but not more than sixty per cent of a polyhydric alcohol ofthe group consisting of glycerine and ethylene glycol partially esterifled with a saturated fatty acid containing twelve or more carbon atoms and not less than about forty per cent of a substantially solid water-soluble salt of a sulfuric reaction prod-- uct of a hgh molecular weight organic compound having more than eight carbon atoms in the alkyl radical, which salt is characterized by its high solubility in water, its high resistance toward the constituents of hard water.

2. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of more than five per cent but not more than sixty per cent of a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a substantially solid watersoluble salt of a compound from the group consisting of the following, in all of which the alkyl radical contains more than eight carbon atoms: sulfonated aliphatic alcohols. sulfated aliphat c alcohols, sulfonated aliphatic hydrocarbons, sulfated aliphatic hydrocarbons, fatty acid esters of hydroxy ethyl sulfonic acid, fatty acid amides of methyl amino ethyl sulfonic acid, fatty acid e ters of dihydroxy propyl sulfonic acid and allcyl ethers of dihydroxy propyl sulfonic ac d.

3. A detergent in bar form substantially free from soap containing predominantly a. mixture consisting of more than five per cent but not more than sixty per cent of a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a sodium salt 01' 'a compound from the group consisting of the following, in all of which the alkyl radical contains more than eight carbon atoms: sulfonated aliphatic alcohols, sulfated aliphatic alcohols, sulfonated aliphatic hydrocarbons, sulfated aliphatic hydrocarbons, fatty acid esters of hydroxy ethyl sulfonic acid,fattyacid amides of methyl amino ethyl sulfonic acid, fatty acid esters of dihydroxy propyl sulfonic acid and alkyl ethers. of dihydroxy propyl sulfonic acid.

4. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of between about eight per cent and about'sixty per cent of glycerin partially esterifled with commercial stearic acid, and not less than about forty per cent of the sodium salt of a compound from the group consisting of the following, in all of which the alkyl radical contains more than eight carbon atoms: sulfonated aliphatic alcohols, sulfated aliphatic alcohols, sulfonated aliphatic hydrocarbons, sulfated aliphatic hydrocarbons, fatty acid esters of hydroxy ethyl sulfonic acid, fatty acidv amides of methyl amino ethyl sulfonic acid, fatty acid esters of dihydroxy propyl sulfonic acid and alkyl ethers of dihydroxy propyl sulfonic acid.

5. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of between about eight per cent and about sixty per cent of a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical and not less than about forty parts of substantially solid water-soluble salts of sulfated higher alcohols obtainable from coconut oil.

6. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of about ninety parts of the sodium salt of the reaction product of concentrated sulfuric acid on the higher alcohols obtainable from coconut oil, and about ten parts of superglycerinated fat prepared from substantially completely hydrogenated cottonseed oil.

7. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of between about eight per cent and about sixty per cent of a saturated superglycerinated fat having at lead-" twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a water insoluble water-soluble salt of a fatty acid ester of hydroxy ethyl sulfonic acid'in which the fatty acid radical contains more than eight carbon atoms. I

8. A detergent in bar form substantially free from soap containing predominantly a mixture consisting of between about eight per cent and about sixty per cent of a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a substantially solid water-soluble salt of the fatty acid amide of methyl amino ethyl sulfonic acid in which the fatty acid radical contains at least eight carbon atoms.

9. A substantially soap-free detergent in bar form comprising? mixture of any of the organic sulfuric reaction products mentioned in claim 2 and a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical, said mixture having the respective active ingredients in the ratio of from about 11.5:1 to about 0.67:1.

10. The process of producing a detergent in bar form and of simultaneously controlling the solubility of a substantially solid water-soluble salt of a sulfuric reaction product of a high molecular weight organic compound having more than eight carbon atoms in the alkyl radical, said salt being characterized by its high solubility in water, its high resistance towardthe constituents of hard water, and its detergent and lathering properties,.which comprises mixing with at least forty parts of said product about ten parts to about sixty parts of a bonding agent consisting essentially of saturated superglycerinatedifat having at least twelve carbon atoms in the fatty acid radical to form 100 parts of mixture and converting the mixture obtained into bar form.

11. In the process of producing a detergent in bar form and of simultaneously controlling the solubility, detergency and lathering properties of a substantially solid water-soluble salt of a sulfuric reaction product of a high molecular weight organic compound having more than eight carbon atoms inthe alkyl radical, said salt being characterized by its high solubility in water, its high resistance toward the constituents of hard water, and its detergent and lathering properties, the steps which comprises adding to and incorporating with at least forty parts of said product five to sixty parts of a bonding agent consisting essentially of a polyhydric alcohol of the group consisting of glycerin and ethylene glycol partially esterified with a saturated fatty acid containing at least twelve carbon atoms in the molecule to form 100 parts of mixture and converting the" mixture obtained into bar form.

12. The process of producing a detergent in bar form and of simultaneously controlling the solubility and lathering properties of a substantially solid water-soluble salt of the sulfated higher alcohols obtainable from an oil of the coconut oil type without affecting the resistance of said salt against precipitation by the constituents of hard water, which comprises adding to and incorporating with at least forty parts of said salt five to sixty parts of a bonding agent consisting essentially of saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical to form 100 parts of mixture and converting the mixture obtained into bar form.

13. A detergent in bar form substantially free from soap containing essentially a mixture of more than five per cent but not more than sixty per cent of a saturated mono-ester of ethylene glycol containing at least twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a substantially solid watersoluble salt of a sulfuric reaction product of a high molecular weight organic compound having more than eight carbon atoms in the alkyl radical, said salt being characterized by its high solubility in water, its high resistance toward precipitation by the constituents of hard water.

radical, which salt is characterized by its high solubility in water, its high resistance toward the constituents of hard water, and its detergent and lathering properties, the said detergent containing said partially esterified polyhydric alcohol within the above range in greater relative proportions in the composition where the product is to be used in hard water, as compared to the proportions where the product is to be used in soft water.

A detergent in bar form, substantially free from soap containing essentially a mixture of more than five per cent but not more than sixty per cent of a saturated superglycerinated fat having at least twelve carbon atoms in the fatty acid radical and not less than about forty per cent of a substantially solid water-soluble salt of a compound of the group consisting of the following, in all.of which the alkyl radical contains more than eight carbon atoms: sulfonatedaliphatlc alcohols, sulfated aliphatic alcohols, sulfonated aliphatic hydrocarbons, sulfated aliphatic hydrocarbons, fatty acid esters of hydroxy ethyl sulfonic acid, fatty acid amides of methyl-amino-ethyl sulfonic acid, fatty acid esters of dihydroxy propyl sulfonlc acid, and alkyl ethers of dihydroxy propyl sulfonic acids, the said detergent containing said superglycerinated fat within the above range in greater relative proportions in the composition where the product is to be used in hard water, as

compared to the proportions where the product is to be used in soft water.

ROBERT A. DUNCAN. 

